Heterocyclic compounds

ABSTRACT

Novel heterocyclic compounds of the formula 
                 
 
wherein, R 1  represents a hydrogen atoms or an alkyl group, A represents an ethylene group which may be substituted by alkyl or a trimethylene group which may be substituted by alkyl, X represents an oxygen or sulfur atom or the group 
                 
 
in which R 2  represents a hydrogen atom of an optionally substituted alkyl, an alkenyl, an alkynyl or an acyl group, and R 3  represents a hydrogen atom or an alkyl group, and Z represents an optionally sibstituted 5-or 6-membered heterocyclic group which contains at least two hetero atoms selected from oxygen, sulfur and nitrogen atoms, or an optionally substituted 3- or 4-pyridyl group.
 
The above defined novel heterocyclic compounds of formula (I) exhibit powerful insecticidal properties.

Notice: More than one reissue application has been filed for the reissueof U.S. Pat. No. 4,849,432. The reissue applications are applicationNos. 08/254,202 (the present application), filed on Jun. 6, 1994;10/067,189, filed on Feb. 4, 2002; 10/067,190, filed on Feb. 4, 2002;10/067,191, filed on Feb. 4, 2002; and 10/167,192, filed on Feb. 4,2002; all of which are divisional reissues of U.S. Pat. No. 4,849,432.

This application is a reissue of U.S. Pat. No. 4,849,432, issued on Jul.18, 1989. Another pending reissue application related to the same patentis U.S. Ser. No. 08/254,202, filed Jun. 6, 1994.

The present invention relates to novel heterocyclic compounds, toprocesses for their preparation, and to their use as insecticides.

It has already been disclosed that certain cyanoimino-substitutedheterocyclic compounds are useful as intermediates for fungicidal,antidiabetic, viral tranquilizing or diuretic active substances (seeDE-OS No. 2,205,745) and also as antiulcer agents (see DE-OS No.3,409,801).

There have now been found novel heterocyclic compounds of the formula(I)

wherein, R¹ represents a hydrogen atom or an alkyl group, A representsan ethylene group which may be substituted by alkyl or a trimethylenegroup which may be substituted by alkyl, X represents an oxygen orsulfur atom or the group

in which R² represents a hydrogen atom or an optionally substitutedalkyl, alkenyl, alkynyl or acyl group, and R³ represents a hydrogen atomor an alkyl group, and Z represents an optionally substituted 5- or6-membered heterocyclic group which contains at least two hetero atomsselected from oxygen, sulfur and nitrogen atoms, or an optionallysubstituted 3- or 4-pyridyl group.

The compounds of the formula (I) are obtained by a process in which

(a) compounds of the formula (II)

wherein A and X are as defined, are reacted with compounds of theformula (III)

wherein R¹ and Z are as defined above, and M¹ represents a halogen atomor the group —OSO₂—M² in which M² represents a lower alkyl group or anaryl group,in the presence of inert solvent, if appropriate in the presence of abase, or

(b) in the case where X in the formula (I) represents an oxygen orsulfur atom or the group

in which R⁴ represents a hydrogen atom, an alkyl group which may besubstituted, an alkenyl group or an alkynyl group, and for which case inthe following formula (IV) X is replaced by the symbol X¹: Compounds ofthe formula (IV)

wherein R¹, A, Z and X¹ are as defined, are reacted with compounds ofthe formula (V)(R′—S)₂C═N—CN   (V)wherein R′ represents a lower alkyl group or a benzyl group, or two R′groups may together represent a lower alkylene group having at least 2carbon atoms and may form a ring together with the adjacent sulfuratoms, in the presence of inert solvents, or

(c) in the case where X in the formula (I) represents the group

in which R² represents an acyl group which may be substituted, and forwhich case in the following formula (VI) R² is replaced by the symbolR⁵: Compounds of the formula (Ib)

wherein R¹, A and Z are as defined above, are reacted with compounds ofthe formula (VI)R⁵—Hal   (VI)wherein R⁵ is as defined above, and Hal represents a halogen atom,in the presence of inert solvents and a base.

The novel heterocyclic compounds of formula (I) exhibit powerfulinsecticidal properties.

Surprisingly, the novel heterocyclic compounds according to theinvention exhibit a substantially greater insecticidal action than thoseknown from the aforesaid prior art, and in particular the compounds haveextremely superior activities as insecticides against stinging andsucking insects typified by hemipterous insects such as aphids,planthoppers and leafhoppers, which have attained resistance toorganophosphate and carbamate insecticides as a result of theirlong-term use.

Among the compounds according to the invention, of the formula (I),preferred compounds are those in which

R¹ represents a hydrogen atom or a methyl group,

A represents an ethylene group which may be substituted by methyl or atrimethylene group which may be substituted by methyl,

X represents an oxygen or sulfur atom or the group

in which R² represents a hydrogen atom, a C₁-C₄ alkyl group which may besubstituted by a substituent selected from halogens, C₁-C₄ alkoxygroups, C₁-C₄ alkylthio groups and cyano, a C₂-C₄ alkenyl group, a C₂-C₄alkynyl group, a pyridylmethyl group which may be substituted by halogenand/or methyl, a benzyl group which may be substituted by halogen and/ormethyl, a formyl group, an alkylcarbonyl group having 1 to 2 carbonatoms in the alkyl moiety which may be substituted by halogen, aphenylcarbonyl group which may be substituted by halogen and/or methyl,an alkoxy- or alkylthiocarbonyl group having 1 to 4 carbon atoms in thealkyl moiety, a phenoxycarbonyl group, a C₁-C₄ alkysulfonyl group whichmay be substituted by halogen or a phenylsulfonyl group which may besubstituted by methyl, and R³ represents a hydrogen atom, and

Z represents a 5- or 6-membered heterocyclic group containing 2 to 3hetero atoms selected from oxygen, sulfur and nitrogen atoms at leastone of which is a nitrogen atom, or a 3-pyridyl group, the heterocyclicgroup and the 3-pyridyl group being optionally substituted by at leastone substituent selected from halogen atoms, alkyl groups having 1 to 4carbon atoms, alkoxy groups having 1 to 4 carbon atoms, alkylthio groupshaving 1 to 4 carbon atoms, haloalkyl groups having 1 to 4 carbon atoms,haloalkoxy groups having 1 to 4 carbon atoms, alkylsulfonyl groupshaving 1 to 4 carbon atoms, a cyano group and a nitro group.

Very particularly preferred compounds of the formula (I) are those inwhich

R¹ represents a hydrogen atom,

A represents an ethylene or trimethylene group,

X represents a sulfur atom or the group —NH, and

Z represents a 5- or 6-membered heterocyclic group containing two heteroatoms selected from oxygen, sulfur and nitrogen atoms at least one ofwhich is a nitrogen atom, or a 3-pyridyl group, the heterocyclic groupand the 3-pyridyl group being optionally substituted by at least onesubstituent selected from a fluorine atom, a chlorine atom, a bromineatom, a methyl group, a methoxy group, a methylthio group, atrifluoromethyl group, a trifluoromethoxy group, a methylsulfonyl group,a cyano group and a nitro group.

The 3-pyridyl group in the definition of Z is structurally synonymouswith 5-pyridyl.

Specific examples of the compounds of formula (I) in accordance withthis invention especially include

-   1-(2-chloro-5-pyridylmethyl)-2-cyanoiminoimidazolidine,-   1-(2-fluoro-5-pyridylmethyl)-2-cyanoiminoimidazolidine,-   1-(2-chloro-5-pyridylmethyl)-2-cyanoiminotetrahydropyrimidine,-   1-(2-methyl-5-pyridylmethyl)-2-cyanoiminoimidazolidine,-   1-(2-chloro-5-thiazolylmethyl)-2-cyanoiminoimidazolidine,-   1-(2-chloro-5-thiazolylmethyl)-2-cyanoiminotetrahydropyrimidine,-   1-(2-methyl-5-pyrazinylmethyl)-2-cyanoiminoimidazolidine,-   1-(2-chloro-5-pyridylmethyl)-2-cyanoiminothiazolidine,-   1-(2-chloro-5-pyridylmethyl)-2-cyanoiminotetrahydro-2H-1,2-thiazine-   1-(2-chloro-5-thiazolylmethyl)-2-cyanoiminothiazolidine,-   1-(2-methyl-5-pyrazinylmethyl)-2-cyanoiminothiazolidine,-   1-(2-methyl-5-thiazolylmethyl)-2-cyanoiminothiazolidine, and-   1-(1,2,5-thiaziazol-3-yl)-2-cyanoiminothiazolidine.

When in process (a) for the production of the compound of formula (I),2-cyanoiminothiazolidine and 2-chloro-5-pyridylmethyl chloride are usedas the starting materials, the reaction is represented by the followingreaction scheme:

When N-(2-chloro-5-pyridylmethyl)ethylenediamine anddimethylcyanodithioimide carbonate are used as the starting materials inprocess (b) for the production of the compound of formula (I), thereaction is represented by the following reaction scheme:

When 1-(2-chloro-5-pyridylmethyl)-2-cyanoiminoimidazolidine and acetylchloride are used as the starting materials is process (c) for theproduction of the compound of formula (I), the reaction is representedby the following reaction scheme:

In process (a), the starting compound of the formula (II) means onebased on the definitions of A and X. Preferably, A and X are synonymouswith the preferred definitions given hereinabove.

The compounds of the formula (II) include known compounds.

2-Cyanoiminoimidazolidine and 2-cyanoiminotetrahydropyridine aredescribed in J. Org. Chem., vol. 38, pages 155-156, and can be easilyobtained by the reaction of dimethyl cyanodithioimidocarbonate withethylenediamine or trimethylenediamine. Likewise, reaction withethylenediamine or trimethylenediamine N-substituted by substituentsother than acyl gives the corresponding3-substituted-2-cyanoiminoimidazolidine or3-substituted-2-cyanoiminotetrahydropyrimidine.

Use of aminoalkanols in place of the alkylenediamines can give thecorresponding oxazolidines or 1,3-oxazine derivatives (JapaneseLaid-Open Patent Publication No. 91064/1973).

2-Cyanoiminothiazolidine is described in Arch. Pharm., vol. 305, pages731-737. Likewise, the reaction of 2-aminopropanethiol with dimethylcyanodithioimidocarbonate gives 2-cyanoiminotetrahydro-1,3-thiazine.

2-Cyanoiminopyrrolidine is described in Khim. Farm. Zh., vol. 19, pages154-158, and can be easily obtained by reacting 2-methoxypyrroline-2 andcyanamide. Similarly, 2-cyanoiminopiperidine is obtained from2-methoxy-3,4,5,6-tetrahydropyridine with cyanamide.

Likewise, the starting compounds of the formula (III) are those based onthe definitions of R¹, Z and M¹. Preferably, R¹, Z are synonymous withthe preferred definitions given hereinabove. M¹ is preferably a chlorineor bromine atom.

The compounds of the formula (III) are described in Japanese PatentApplication Nos. 18627/1985, 18628/1985, and 106853/1985 filed by thesame applicants as the present one. Specific examples include

-   2-fluoro-5-pyridylmethyl chloride,-   2-chloro-5-pyridylmethyl chloride,-   2-bromo-5-pyridylmethyl chloride,-   2-methyl-5-pyridylmethyl chloride,-   2-chloro-5-thiazolylmethyl chloride,-   2-methyl-5-pyrazinylmethyl chloride,-   2-methyl-5-oxazolylmethyl chloride,-   1,2,5-thiaziazol-3-ylmethyl chloride,-   3-methyl-5-isoxazolylmethyl chloride, and-   2-chloro-5-pyrimidinylmethyl chloride.

In process (b), the starting compounds of the formula (IV) are thosebased on the definitions of R¹, A and Z, and R¹, A and Z are synonymouswith the preferred definitions given hereinabove.

The compounds of the formula (IV) are described in Japanese PatentApplications Nos. 18627/1985, 18628/1985, 23683/1985, 106853/1985, and219082/1985. Specific examples include

-   N-(2-chloro-5-pyridylmethyl)-ethylenediamine or trimethylenediamine,-   N-(2-fluoro-5-pyridylmethyl)-ethylenediamine or trimethylenediamine,-   N-(2-methyl-5-pyridylmethyl)-ethylenediamine or trimethylenediamine,-   N-(2-methyl-5-thiazolylmethyl)-ethylenediamine or    trimethylenediamine, and-   N-(2-methyl-5-pyrazinylmethyl)-ethylenediamine or    trimethylenediamine.    Other examples include-   2-(2-chloro-5-pyridylmethyl)aminoethanethiol,-   3-(2-chloro-5-pyridylmethyl)aminopropenethiol,-   2-(2-chloro-5-thiazolylmethyl)aminoethanethiol, and-   2-(2-methyl-5-pyrazinylmethyl)aminoethanethiol.

The starting compounds of the formula (V) are described in J. Org.Chem., vol. 32, pages 1566-1572.

In process (c), the starting compounds of the formula (Ib) are includedwithin the compounds of formula (I) in accordance with this inventionwhich can be produced by process (a) or (b).

The starting compounds of the formula (VI) are well known in the fieldof organic chemistry, and their specific examples include propionylchloride, acetyl chloride, chloroacetyl chloride, methylsulfonylchloride, tosyl chloride and methoxycarbonyl chloride.

In the practice of process (a), suitable diluents are used which includeall inert organic solvents.

Examples of the diluent include aliphatic, alicyclic and aromatichydrocarbons (optionally chlorinated) such as hexane, cyclohexane,petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride,chloroform, carbon tetrachloride, ethylene chloride, trichloroethyleneand chlorobenzene; ethers such as diethyl ether, methyl ethyl ether,di-isopropyl ether, dibutyl ether, propylene oxide, dioxane andtetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methylisopropyl ketone and methyl isobutyl ketone; nitriles such asacetonitrile, propionitrile and acrylonitrile, esters such as ethylacetate and amyl acetate; acid amides such as dimethylformamide anddimethylacetamide; and sulfones and sulfoxides such as dimethylsulfoxide and sulfolane.

The reaction of process (a) may be carried out in the presence of abase. Examples of the base are alkali metal hydrides such as sodiumhydride and potassium hydride, and hydroxides and carbonates of alkalimetals.

Process (a) can be carried out over a broad temperature range, forexample between about 0° and about 100° C., preferably between about 10°and about 80° C. Desirably, the reaction is carried out underatmospheric pressure, but it is also possible to operate under reducedpressure.

In the practice of process (a), for example, 1 mole of the compounds ofthe formula (II) is reacted with 1 to about 1.2 moles, preferably 1 toabout 1.1 moles, of the compounds of the formula (III) in an inertsolvent such as dimethylformamide in the presence of a base to give thedesired compound of general formula (I).

In the practice of process (b), suitable diluents include water andalcohols in addition to the inert organic solvents illustrated forprocess (a).

Process (b) can be carried out over a broad temperature range, forexample between 0° C. and the boiling point of the reaction mixture,preferably between about 0° C. and about 100° C. Preferably, thereaction is carried out under atmospheric pressure, but can also becarried out under elevated or reduced pressure.

In the practice of process (b), for example, 1 mole of the compound offormula (IV) is reacted with 1 to about 1.2 moles, preferably 1 to about1.1 moles, of the compound of formula (v) in an inert solvent such as analcohol (e.g., methanol or ethanol) until the generation of mercaptanceases, to obtain the desired novel compound of general formula (I).

In the practice of process (c), suitable diluents may be the same asthose illustrated above for process (a). Process (c) may be carried outin the presence of a base. The same alkali metal hydrides illustratedabove for process (a) may be cited as examples of such a base.

Process (c) may be practiced over a broad temperature range, preferablybetween 0° C. and the boiling point of the mixture, especially between0° C. and 100° C. Desirably, the reaction is carried out underatmospheric pressure, but may be carried out under elevated or reducedpressure conditions.

The compounds of the formula (I) in accordance with this invention maybe present in the form of salts such as inorganic acid salts,sulfonates, organic acid salts and metal salts. Accordingly, the novelheterocyclic compounds of the formula (I) in this invention are meant todenote their salts as well.

The active compounds as well tolerated by plants, have a favourablelevel of toxicity to warm-blooded animals, and can be used for combatingarthropod pests, especially insects which are encountered inagriculture, in forestry, in the protection of stored products and ofmaterials, and in the hygiene field. They are active against normallysensitive and resistant species and against all or some stages ofdevelopment. The above-mentioned pests include:

from the class of the Isopoda Diplopoda, for example Oniscus Asellus,Armadillidium vulgare and Porcellio scaber;

from the class of the Diplopoda, for example Blaniulus guttulatus;

from the class of the Chilopoda, for example Geophilus carpophagus andScutigera spec.;

from the class of the Symphyla, for example Scutigerella immaculata;

from the order of the Thysanura, for example Lepisma saccharina;

from the order of the Collembola, for example Onychiurus armatus;

from the order of the Orthoptera; for example Blatta orientalils,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria;

from the order of the Dermaptera, for example Forficula auricularia;

from the order of the Isoptera, for example Reticulitermes spp.;

from the order of the Anoplura, for example Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.;

from the order of the Mallophaga, for example Trichodectes spp. andDamalinea spp.;

from the order of the Thysanoptera, for example Hercinothrips femoralisand Thrips tabaci,

from the order of the Heteroptera, for example Eurygaster spp.,Dysdercus intermedius, Piesma guadrata, Climex lectularius, Rhodniusprolixus and Triatoma spp.;

from the order of the Homoptera, for example Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantit, Aspidiotushederae, Pseudococcus spp. and Psylla spp.;

from the order of the Lepidoptera, for example Pectinophora gossypiella,Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella,Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria,Euproctis chrysorrhoea, Lymantria spp., Buccalatrix thurberiella,Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Eariasinsulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolisflammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsapomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestiakuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana,Choristoneura fumiferana, Clysia ambiguella, Homona magnanima andTortrix viridana;

from the order of the Coleoptera, from example Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelidesobtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsadecemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodeschrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilussurinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus,Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctusspp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbiumpsylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderusspp., Melolontha melolontha, Amphimallon solstitialis and Costelytrazealandica;

from the order of the Hymenoptera for example Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.,

from the order of the Diptera, for example Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa;

In the field of veterinary medicine, the novel compounds of thisinvention are effective against various noxious animal parasites (endo-and ecto-parasites) such as insects and worms.

Examples of such animal parasites are insects such as Gastrophilus spp.,Stomoxys spp., Trichodectes spp., Rhodnius spp., and Ctenocephalidescanis.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, natural and synthetic materials impregnated withactive compound, very fine capsules in polymeric substances, coatingcompositions for use on seed, and formulations used with burningequipment, such as fumigating cartridges, fumigating cans and fumigatingcoils, as well as ULV cold mist and warm mist formulations.

These formulations may be produced in known manner, for example bymixing the active compounds with extenders, that is to say liquid orliquefied gaseous or solid diluents or carriers, optionally with the useof surface-active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents.

As liquid solvents diluents or carriers, there are suitable in the main,aromatic hydrocarbons, such as xylene, toluene or alkyl napthalenes,chlorinated aromatic or chlorinated aliphatic hydrocarbons, such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons, such as cyclohexane or paraffins, for example mineral oilfractions, alcohols, such as butanol or glycol as well as their ethersand esters, ketones, such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, or strongly polar solvents, such asdimethylformamide and dimethyl-sulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperature and under normal pressure, for exampleaerosol propellants, such as halogenated hydrocarbons as well as butane,propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates. As solid carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, corn cobs and tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. Dispersing agents include, for example,lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulation.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs or metal phthalocyaninedyestuffs, and trace nutrients, such as salt of iron, manganese boron,copper, cobalt, molybdenum and zinc.

The formulation in general contain from 0.1 to 95 per cent by weight ofactive compound, preferably from 0.5 to 90 per cent by weight of activecompound.

The active compounds according to the invention can be present in theircommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, baits, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphates, carbamates, carboxylates, chlorinatedhydrocarbons, phenylureas, substances produced by microorganisms.

The active compounds according to the invention can furthermore bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergisticagents. Synergistic agent are compounds which increase the action of theactive compounds, without it being necessary for the synergistic agentadded to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to100% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompounds are distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates. Thefollowing examples illustrate the present invention more specifically.It should be understood however that the invention is in no way limitedto these examples alone.

Production Example EXAMPLE 1

N-(2-chloro-5-pyridylmethyl)ethylenediamine (3.7 g) and dimethylcyanodithioimidocarbonate (1.3 g) were added to 50 ml of ethanol, andthe mixture was gradually heated with stirring and subsequently refluxedfor 3 hours. After the reaction, ethanol was distilled off under reducedpressure, whereupon the residue solidified. The solidified residue waspulverized and washed with a mixture of ether and a small amount ofethanol. The amount of the product yielded after drying was 3.5 g. m.p.167°-170° C.

EXAMPLE 2

N-(2-chloro-5-pyridylmethyl)cysteamine (2.0 g) and dimethylcyanodithioimidocarbonate (1.3 g) were added to 50 ml of ethanol. In astream of nitrogen gas, the mixture was refluxed for 8 hours withstirring. After the reaction, about ⅔ of ethanol was distilled off underreduced pressure. When the residue was left to stand at roomtemperature, the final product precipitated as crystals. The crystalswere collected by filtration, washed with ether and dried. The amountyielded was 2.4 g. m.p. 128°-129° C.

EXAMPLE 3

A mixture of 2-cyanoiminothiazolidine (2.5 g), anhydrous potassiumcarbonate (3.0 g), 2-chloro-5-chloromethylthiazole (3.3 g) and dryacetonitrile was refluxed for 3 hours with good stirring. After thereaction, acetonitrile was distilled off under reduced pressure, anddichloromethane was added to the residue. The mixture was washed withwater and a 1% aqueous solution of sodium hydroxide. The dichloromethanelayer was dried and concentrated. The precipitate was collected byfiltration, and dried. The amount yielded was 3.3 g. mp. 145°-146° C.

EXAMPLE 4

2-Cyanoiminoimidazolidine (2.2 g) was dissolved in 25 ml of drydimethylformamide, and sodium hydride (1 g) was added little by littleat less than 10° C. and the mixture was stirred at 10° C. until thegeneration of hydrogen ceased. Then, a solution of2-chloromethyl-5-methylpyrazine (2.8 g) in dimethylformamide (10 ml) wasadded dropwise at 10° C. After the addition, the mixture was stirred atroom temperature for 1 hour. Ice water was added to the mixture, and thepH of the aqueous solution was adjusted to 7. The aqueous layer wasextracted with dichloromethane, and the dichloromethane layer was washedwith water and dried. After concentrating dichloromethane, the remainingsolid was recrystallized from dilute ethanol to give 1.8 g of the finalproduct. mp. 144°-147° C.

EXAMPLE 5

1-(2-Chloro-5-pyridylmethyl)-2-cyanoiminoimidazolidine (2.4 g) wasdissolved in 30 ml of dry dimethylformamide, and sodium hydride (0.26 g)was added at 10° C. The mixture was stirred at room temperature untilthe generation of hydrogen ceased. Then, benzoyl chloride (1.4 g) wasadded, and the mixture was stirred at 40° C. for 30 minutes, and pouredinto ice water. The aqueous layer was extracted with dichloromethane.The dichloromethane layer was washed with water, and dichloromethane wasconcentrated. The residue was purified by silica gel columnchromatography to give the final product. The amount yielded was 1.3 g.mp. 158°-161° C.

The compounds shown in Table 1 can be prepared in the same way asexemplified in Examples 1 to 5. Table 1 also discloses the compoundsobtained in Examples 1 to 5.

TABLE 1

Compound No.

A X 1

—CH₂CH₂— NH 2

—CH₂CH₂— NH mp. 191-193° C. 3

—(CH₂)₃— NH mp. 214-216° C. 4

—CH₂CH₂— NH mp. 154-157° C. 5

—CH₂CH₂— NH mp. 167-170° C. 6

—CH₂CH₃— NH 7

NH mp. 155-160° C. 8

—(CH₂)₃— NH   mp. 166-167.5° C. 9

—CH₂CH₂— NH 10

—CH₂CH₂— NH 11

—(CH₂)₃— NH mp. 184-188° C. 12

NH 13

—CH₂CH₂— NH 14

—CH₂CH₂— NH 15

—CH₂CH₂— NH 16

—CH₂CH₂— NH 17

—CH₂CH₂— NH 18

—CH₂CH₂— NH 19

—(CH₂)₃— NH 20

—CH₂CH₂— NH 21

—CH₂CH₂— NH 22

—CH₂CH₂— NH 23

—(CH₂)₃— NH 24

—(CH₂)₃— NH 25

—CH₂CH₂— NH mp. 161-162° C. 26

—CH₂CH₂— NH 27

—(CH₂)₃— NH mp. 182-185° C. 28

—(CH₂)₃— NH 29

NH mp. 224-227° C. 30

—CH₂CH₂— NH 31

—CH₂CH₂— NH 32

—CH₂CH₂— NH 33

—(CH₂)₃— NH mp. 145-148° C. 34

—CH₂CH₂— NH mp. 129-131° C. 35

—(CH₂)₃— NH 36

—CH₂CH₂— NH 37

—(CH₂)₃— NH 38

—CH₂CH₂— NH 39

—(CH₂)₃— NH mp. 137-140° C. 40

—(CH₂)₃— NH 41

—(CH₂)₃— NH 42

—CH₂CH₂— NH 43

—(CH₂)₃— NH 44

—CH₂CH₂— NH 45

—CH₂CH₂— NH 46

—CH₂CH₂— NH 47

—CH₂CH₂— NH 48

—(CH₂)₃— NH 49

—CH₂CH₂— NH 50

—CH₂CH₂— NH 51

—(CH₂)₃— NH mp. 185-188° C. 52

—CH₂CH₂— NH 53

—CH₂CH₂— NH 54

—CH₂CH₂— NH mp. 144-147° C. 55

—CH₂CH₂— N—CHO 56

—CH₂CH₂— N—COCH₃ n_(D) ²⁰ 1.5895 57

—CH₂CH₂—

mp. 53-55° C. 58

—CH₂CH₂— N—COC(CH₃)₃ 59

—CH₂CH₂—

60

—(CH₂)₃—

61

—(CH₂)₃— N—COOC₂H₅ 62

—CH₂CH₂—

63

—CH₂CH₂— S 64

—CH₂CH₂— S mp. 117-120° C. 65

—CH₂CH₂— S mp. 128-129° C. 66

—CH₂CH₂— S 67

—(CH₂)₃— S mp. 124-125° C. 68

—CH₂CH₂— S 69

—CH₂CH₂— S mp. 145-146° C. 70

—(CH₂)₃— S 71

—(CH₂)₃— S 72

—(CH₂)₃— S 73

—CH₂CH₂— S mp. 153-157° C. 74

—(CH₂)₃— S 75

—CH₂CH₂— S 76

—CH₂CH₂— S 77

—CH₂CH₂— S 78

—(CH₂)₃— S 79

—CH₂CH₂— S mp. 132-135° C. 80

—CH₂CH₂— O 81

—CH₂CH₂— O 82

—CH₂CH₂— O 83

—CH₂CH₂— O mp. 113-114° C. 84

—(CH₂)₃— O 85

—CH₂CH₂— O 86

—CH₂CH₂— O 87

—(CH₂)₃— O 88

—CH₂CH₂— N—COCCl₃ 89

—CH₂CH₂—

mp. 158-161° C. 90

—CH₂CH₂— N—COOCH₃ 91

—CH₂CH₂—

92

—CH₂CH₂— N—COCH₃ 93

—CH₂CH₂— N—COOCH₃ 94

—(CH₂)₃— N—COSC₂H₅ 95

—(CH₂)₃—

96

—CH₂CH₂— N—COC₂H₅ 97

—CH₂CH₂— S mp. 138-140° C. 98

—(CH₂)₃— S 99

—CH₂CH₂— O 100

—CH₂CH₂— O 101

—CH₂CH₂— O 102

—(CH₂)₃— O 103

—CH₂CH₂— O mp. 130-134° C. 104

—CH₂CH₂— CH₂ 105

—CH₂CH₂— CH₂ 106

—CH₂CH₂— CH—CH₃ 107

—(CH₂)₃— CH₂ mp. 74-76° C. 108

—CH₂CH₂— CH₂ 109

—CH₂CH₂— CH₂ 110

—CH₂CH₂— CH₂ 111

—(CH₂)₃— CH₂ mp. 122-125° C. 112

—(CH₂)₃— CH₂ 113

—CH₂CH₂— CH₂ 114

—CH₂CH₂— O 115

—CH₂CH₂— O 116

—(CH₂)₃— NH mp. 185-190° C. 117

—CH₂CH₂— N—CH₃ mp. 101-103° C. 118

—CH₂CH₂— N—CH₂CN n_(D) ²⁰ 1.6015 119

—CH₂CH₂— N—CH₂CF₃ 120

—(CH₂)₃— N—CH₂CH₂OCH₃ 121

—CH₂CH₂— N—CH₂CH₂SC₂H₅ 122

—CH₂CH₂—

n_(D) ²⁰ 1.6145 123

—CH₂CH₂—

124

—CH₂CH₂— N—CH₂CH═CH₂ 125

—CH₂CH₂— N—CH₂C≡CH 126

—CH₂CH₂— N—CH₂CH₂CN 127

—(CH₂)₃— S mp. 141-145° C. 128

—CH₂CH₂— CH₂ mp. 85-90° C. 129

—CH₂CH₂—

mp. 161-163° C. 130

—CH₂CH₂— N—COOC₂H₅ n_(D) ²⁰ 1.5880 131

mp. 82-85° C. 132

—(CH₂)₃— N—CH₂C≡CH n_(D) ²⁰ 1.5667 133

—CH₂CH₂—

n_(D) ²⁰ 1.5446 134

O mp. 119-121° C.

Use Examples

Comparison compounds of the closest state of the art:

(described in Japanese Laid-Open Patent Publication No. 91064)

(described in the above-cited patent document)

(described in Japanese Laid-Open Patent Publication No. 196877/1984)

EXAMPLE 6 (biological test) Test on organophosphate-resistant green riceleafhoppers (Nephotettix cincticeps)

Preparation of a test chemical

Solvent: 3 parts by weight of xylene

Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether

To prepare a preparation of a suitable active compound, 1 part by weightof the active compound was mixed with the above amount of the solventcontaining the above amount of the emulsifier, and the mixture wasdiluted with water to a predetermined concentration.

Testing method

A water dilution of each of the active compounds in a predeterminedconcentration prepared as above was sprayed onto rice plants, about 10cm tall, grown in pots having a diameter of 12 cm at a rate of 10 ml perpot. The sprayed chemical was dried, and a wire net having a diameter of7 cm and a height of 14 cm was put over each of the pots, and 30 femaleimagoes of rice leafhopper of a strain having resistance toorganophosphate chemicals were released into the net. The pots wereplaced in a constant-temperature chamber. Two days later, the number ofdead insects was examined, and the kill ratio was calculated.

Compared with comparison compounds W-1, W-2 and Q 2 for example thefollowing compounds according to the invention exhibited a considerablybetter efficacy: Compound Nos. 4, 5, 8, 9, 25, 27, 54, 65, 67, 69, 79.

EXAMPLE 7 (biological test) Test on planthoppers

Testing method

A water dilution of each of the active compounds in a predeterminedconcentration prepared as in the preceding example was sprayed onto riceplants, 10 cm tall, grown in pots having a diameter of 12 cm at a rateof 10 ml per pot. The sprayed chemical was dried, and a wire net havinga diameter of 7 cm and a height of 14 cm was put over each of the pots,and 30 female imagoes of brown planthopper (Nilaparvata lugens) of astrain having resistance to organophosphate chemicals were released intothe net and the pots were placed in a constant temperature chamber. Twodays later, the number of dead insects was examined, and the kill ratiowas calculated.

In the same way as above, the kill ratio on white-backed planthopper(Sogatella furcifera) and organophosphate-resistant smaller brownplanthopper (Laodelphax striatellus) was calculated.

Compared with comparison compounds W-1, W-2 and Q-1 for example thefollowing compounds according to the invention exhibited a considerablybetter efficacy against brown planthoppers, brown smaller planthoppersand white-backed planthoppers: Compounds No. 4, 5, 8, 9, 25, 27, 65, 67.

EXAMPLE 8 (biological test)

Test on green peach aphids (Myzus persicae) having resistance toorganophosphate and carbamate chemicals

Testing method

Bred green peach aphids having resistance to organophosphates andcarbamates were inoculated on eggplant (black elongate variety)seedlings, about 20 cm tall, grown in unglazed pots having a diameter of15 cm at a rate of about 200 per seedling. One day after theinoculation, a water dilution of each of the active compounds in apredetermined concentration prepared as in Example 6 was sprayed insufficient amounts by means of a spray gun. After the spraying, the potswere left to stand in a greenhouse kept at 28° C. Twenty-four hoursafter the spraying, the kill ratio was calculated. The above test wascarried out through two replicates.

Compared with comparison compounds W-1, W-2 and Q-2 for example thefollowing compounds according to the invention exhibited a considerablybetter efficacy against Myzus persicae: Compounds No. 4, 5, 25, 27, 65,67, 69.

The biological tests shown in Examples 6, 7 and 8 are only typicalexamples of the insecticidal use of the compounds of this invention. Thecompounds of this invention shown herein are typical examples, and theutility of the invention is not to be limited to these examples alone.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

1. A heterocyclic compound of the formula

wherein R¹ represents a hydrogen atom or a methyl group, A represents anethylene group which may be substituted by methyl, X represents anoxygen or sulfur atom or the group

in which R² represents a hydrogen atom, a C₁-C₄ alkyl group which may besubstituted by a substituent selected from halogens, C₁-C₄ alkoxygroups, C₁-C₄ alkylthio groups and cyano, a C₂-C₄ alkenyl group, a C₂-C₄alkynyl group, a pyridylmethyl group which may be substituted by halogenand/or methyl, a benzyl group which may be substituted by halogen and/ormethyl, a formyl group, an alkylcarbonyl group having 1 to 2 carbonatoms in the alkyl moiety which may be substituted by halogen, aphenylcarbonyl group which may be substituted by halogen and/or methyl,an alkoxy or alkylthiocarbonyl group having 1 to 4 carbon atoms in thealkyl moiety, a phenoxycarbonyl group, a C₁-C₄ alkylsulfonyl group whichmay be substituted by halogen or a phenylsulfonyl group which may besubstituted by methyl, R³ represents a hydrogen atom or a C₁-C₇ alkylgroup, and Z represents a 3-pyridyl group or a 4-pyridyl groupoptionally substituted by at least one substituent selected from halogenatoms, alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1to 4 carbon atoms, alkylthio groups having 1 to 4 carbon atoms,haloalkyl groups having 1 to 4 carbon atoms, haloalkoxy groups having 1to 4 carbon atoms, alkylsulfonyl groups having 1 to 4 carbon atoms, acyano group and a nitro group.
 2. A compound according to claim 1,wherein R¹ represents a hydrogen atom, A represents an ethylene group, Xrepresents a sulfur atom or the group

and Z represents a 3-pyridyl group or a 4-pyridyl group optionallysubstituted by at least one substituent selected from a flourine atom, achlorine atom, a bromine atom, a methyl group, a methoxy group, amethylthio group, a trifluoromethyl group, a trifluoromethoxy group, amethylsulfonyl group, a cyano group and a nitro group.
 3. A compoundaccording to claim 1, wherein such compound is1-(2-chloro-5-pyridylmethyl)-2-cyanoiminoimidazolidine of the formula


4. A compound according to claim 1, wherein such compound is1-(2-fluoro-5-pyridylmethyl)-2-cyanoiminoimidazolidine of the formula


5. A compound according to claim 1, wherein such compound is1-(2-methyl-5-pyridylmethyl)-2-cyanoiminoimidazolidine of the formula


6. A compound according to claim 1, wherein such compound is1-(2-chloro-5-pyridylmethyl)-2-cyanoiminothiazolidine of the formula


7. An insecticidal composition comprising an insecticidally effectiveamount of a compound according to claim 1 and a diluent.
 8. A method ofcombating insects which comprises applying to such insects or to aninsect habitat an insecticidally effective amount of a compoundaccording to claim
 1. 9. The method according to claim 8, wherein suchcompound is 1-(2-chloro-5-pyridylmethyl)-2-cyanoiminoimidazolidine,1-(2-fluoro-5-pyridylmethyl)-2-cyanoiminoimidazolidine,1-(2-chloro-5-pyridylmethyl)-2-cyanoiminotetrahydropyrimidine,1-(2-methyl-5-pyridylmethyl)-2-cyanoiminoimidazolidine,1-(2-chloro-5-thiazolylmethyl)-2-cyanoiminoimidazolidine,1-(2-chloro-5-thiazolylmethyl)-2-cyanoiminotetrahydropyrimidine,1-(2-methyl-5-pyrazinylmethyl)-2-cyanoiminoimidazolidine,1-(2-chloro-5-pyridylmethyl)-2-cyanoiminothiazolidine,1-(2-chloro-5-pyridylmethyl)-2-cyanoiminotetrahydro-2H-1,2-thiazine1-(2-chloro-5-thiazolylmethyl)-2-cyanoiminothiazolidine,1-(2-methyl-5-pyrazinylmethyl)-2-cyanoiminothiazolidine,1-(2-methyl-5-thiazolylmethyl)-2-cyanoiminothiazolidine, or1-(1,2,5-thiaziazol-3-yl)-2-cyanoiminothiazolidine.